Rydberg states of chloroform studied by VUV photoabsorption spectroscopy

The VUV photoabsorption spectra of CHCl3 and CDCl3 in the energy region 6.2–11.8eV (50,000–95,000cm−1) have been investigated using synchrotron radiation from the Indus-1 source. Rydberg series converging to the first four ionization limits at 11.48, 11.91, 12.01 and 12.85eV corresponding to excitation from the 1a2, 4a1, 4e, 3e, orbitals of CHCl3 respectively are identified and analyzed. Quantum defect values are observed to be consistent with excitation from the chlorine lone pair orbitals. Vibrational progressions observed in the region of 72,500–76,500cm−1 have been reassigned to ν3 and combination modes of ν3+ν6 belonging to the 1a2→4p transition in contrast to earlier studies where they were assigned to a ν3 progression superimposed on the 3e→4p Rydberg transition. The assignments are further confirmed based on isotopic substitution studies on CDCl3 whose VUV photoabsorption spectrum is reported here for the first time. The frequencies of the ν3 and ν6 modes in the 4p Rydberg state of CHCl3 (CDCl3) are proposed to be ~454 (409)cm−1 and~130 (129)cm−1 respectively based on the vibronic analysis. DFT calculations of neutral and ionic ground state vibrational frequencies support the vibronic analysis. Experimental spectrum is found to be in good agreement with that predicted by TDDFT calculations. This work presents a consolidated analysis of the VUV photoabsorption spectrum of chloroform. •VUV photoabsorption spectra of CHCl3 and CDCl3 studied using synchrotron radiation.•Quantum defect analysis of Rydberg series converging to first four ionization limits.•Vibronic bands in 72,500–76,500cm−1 region assigned to 1a2→4p Rydberg transition.•Vibrational progressions assigned to ν3 and ν3+ν6 using ab initio calculations.•Excellent agreement of TDDFT vertical excited energies with experimental spectrum.